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WO2009001365A1 - Procédé de fabrication de sels de titane - Google Patents

Procédé de fabrication de sels de titane Download PDF

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Publication number
WO2009001365A1
WO2009001365A1 PCT/IL2008/000889 IL2008000889W WO2009001365A1 WO 2009001365 A1 WO2009001365 A1 WO 2009001365A1 IL 2008000889 W IL2008000889 W IL 2008000889W WO 2009001365 A1 WO2009001365 A1 WO 2009001365A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium
tix
salt
group
tiox
Prior art date
Application number
PCT/IL2008/000889
Other languages
English (en)
Other versions
WO2009001365A4 (fr
Inventor
Asher Vitner
Original Assignee
Asher Vitner Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from IL184311A external-priority patent/IL184311A0/en
Application filed by Asher Vitner Ltd. filed Critical Asher Vitner Ltd.
Priority to EP08763645A priority Critical patent/EP2173662A1/fr
Priority to US12/666,947 priority patent/US8628736B2/en
Priority to CN2008801005503A priority patent/CN101918318A/zh
Publication of WO2009001365A1 publication Critical patent/WO2009001365A1/fr
Publication of WO2009001365A4 publication Critical patent/WO2009001365A4/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/02—Halides of titanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/02—Halides of titanium
    • C01G23/022—Titanium tetrachloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/02—Halides of titanium
    • C01G23/026—Titanium trichloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/02—Halides of titanium
    • C01G23/028—Titanium fluoride

Definitions

  • the invention is directed to a process for the industrial production of titanium salts such as TiCI 4 , TiBr 4 , other titanium halide salts, titanium salts of mono-valent anions (TiX 4 ), titanium salts of di-valent anions - TiX 2 and titanium salts of tri-valent anions Ti 3 X 4 .
  • TiX 4 mono-valent anions
  • TiX 2 titanium salts of di-valent anions
  • Ti 3 X 4 titanium salts of tri-valent anions
  • Titanium tetrachloride is typically produced by reacting titanium dioxide containing ore with chlorine in the presence of coke at a temperature of approximately 1000 0 C in a fluidized bed reactor.
  • the off-gas mainly contains the product TiCI 4 gas, together with CO gas, CO 2 gas and N 2 gas.
  • the chlorination step ore and coke should be available in large amounts with respect to chlorine to ensure a complete reaction of chlorine.
  • the chlorination process results in the release of a variety of contaminates, such as CO, CO 2 and other contaminates such as dioxins, into the atmosphere, which release must be prevented.
  • Titanium tetra halides can be produced by thermal conversion of titanium salts such as TiCI 3 , TiBr 3 or TiOCI 2 .
  • the raw materials for such production are expensive and are usually produced for titanium tetra halides themselves by reduction or hydrolysis:
  • Titanyl chloride of high purity can be produced by carefully reacting TiCI 4 with water.
  • the cost of highly purified TiOCI 2 is higher than that of TiCI 4 .
  • TiOCI 2 is prohibitively expensive for the industrial production of TiCI 4 .
  • Titanic acid is usually used for the production of TiO 2 . It is produced in large amounts in the sulfate process. In this industrial production, the separation is done by heating a dilute solution at a relatively high temperature and in the presence of other contaminates. Since the resultant product was converted afterwards in the calcinations stage to TiO 2 , no attempt was made to produce it in a way in which it can be dissolved.
  • titanic acid can be precipitated in such a way that the produced titanic acid is easily dissolved in acid to get concentrated titanyl salt solutions.
  • titanic acid is precipitated from the solution obtained by the leaching of llmenite. It is precipitated from the above solution by heating a non-pure solution that results in a product with a purity that is much lower than needed for the production of TiCI 4 and titanium metal.
  • the obtained product has a relatively low solubility in solution at low amount of acid halide (HX) solutions.
  • HX acid halide
  • Such a process comprises the precipitation of titanic acid to produce titanic acid, dissolution of the titanic acid in acid solution and decomposition of a titanium salt at a temperature higher than 17O 0 C.
  • the main use of the TiCI 4 and other titanium salts produced, according to the present invention, is as a raw material for the titanium metal industry.
  • a method for the industrial production of titanium (IV) containing products TP by thermal conversion of titanium salts comprising the steps of: i. Precipitation of titanic acid from a solution comprising titanium salt TP1 ; ii. Production of a titanium containing product TP2 from a media comprising said titanic acid and an acid; iii. Thermal conversion of titanium containing product TP3 to a titanium salt TP at temperature higher than 170 0 C.
  • the method further includes the production of titanium metal from said titanium product TP during the thermal conversion stage of TP3.
  • the method relates to the production of other titanium salts by the thermal conversion of TP3.
  • HX relates to a strong acid having a pK value lower than 2.5 and X relates to the anion of that acid and of the various titanium salts.
  • X is chloride and TP is TiCI 4 .
  • anion X is selected from the group consisting of halides and monovalent anions (wherein TP is TiX 4 ), divalent anions (wherein TP is TiX 2 ) or trivalent anions (wherein TP is Ti 3 X 4 ) and any combination thereof.
  • the process is comprised of at least 3 stages:
  • the precipitation of titanic acid from titanium salt containing solution - the titanium containing salt of Stage 1 will be referred to as TP1.
  • titanic acid relates to TiO(OH) 2 , its hydrates (TiO(OH) 2 * (H 2 O) n or solvates (TiO(OH) 2 * (HX) n , (TiO(OH) 2 * (solvent) n , and also to any dehydrated or polymerized form of TiO(OH) 2
  • the main production of titanic acid is performed via the procedure that includes:
  • the titanyl salt TP1 is produced from a solution obtained by the leaching of llmenite or other titanium containing ores.
  • the titanyl salt TP1 is further purified to give a solution with a ratio between titanium to all polyvalent cations of higher than 97%.
  • the ratio between titanium to all polyvalent cations is higher than 99% and in a more preferred embodiment the ratio between titanium to all polyvalent cations is higher than 99.9%.
  • the purification of the titanyl salt may be done using one or more conventional methods such as Extraction, Crystallization, and Separation upon ion exchangers or any other purification method.
  • the titanyl salt TP1 is further purified by the crystallization of its double salt.
  • the double salt is selected from the group comprising of titanyl Monovalent-cation anions.
  • the titanyl double salt is titanyl ammonium sulfate. The precipitation of titanic acid from said double salt solution is done by adding a base to increase the pH.
  • the purification of the titanyl salt is done by it crystallization from the solution obtained after leaching.
  • the crystallization is induced using a method selected from cooling, evaporation, addition of an anti solvent and the combination thereof.
  • the anti solvent is an acid.
  • the acid is H 2 SO 4 .
  • titanic acid dissolves more easily in acid solution at low temperature than from solution at higher temperature.
  • the titanic acid is precipitated from a solution at temperature lower than 9O 0 C.
  • the titanic acid is precipitated from a solution at temperature lower than 50 0 C, and in a more preferred embodiment the titanic acid is precipitated from a solution at temperature lower than 3O 0 C.
  • titanic acid that is precipitated by the addition of a base to the titanyl salt TP1 solution dissolves more easily if it the solution is well stirred and its solubility in acidic solution is better it is precipitated from a lower pH level solution than from higher pH level.
  • a base to the titanyl salt TP1 solution
  • its solubility in acidic solution is better it is precipitated from a lower pH level solution than from higher pH level.
  • sulfate salts in solution can contribute to the production titanic acid with high solubility.
  • the titanic acid is precipitated by adding a base solution to a well stirred solution.
  • the titanic acid is precipitated from a buffered solution.
  • the buffered solution contains a sulfate ion or other acidic buffers.
  • the concentration of the buffer solution is higher than 10%. In a more preferred embodiment, the concentration of the buffer solution is higher that 20%. In the best embodiment the concentration of the buffer solution is close to its saturation concentration.
  • the titanic acid is precipitated by adding a base solution at concentration lower than 3M to TP1 solution.
  • the base solution is at concentration lower than 1M and in a more preferred embodiment the concentration of the base is lower than 0.5M.
  • the base solution is a solution comprising of ammonia. In a more preferred embodiment the base solution is a solution comprising of ammonia and ammonium salt.
  • solubility of titanium salts in many solvents is surprisingly high.
  • concentration of titanyl chloride in methanol solution is higher than 25%.
  • solubility of titanium salts in the various alkanols is high enough to enable the industrial use of such solvents for the dissolution of the titanium salts and the precipitation of dry titanic acid from such solutions.
  • the solvents one may choose from the group of alkanols, hydrophilic solvents such as acetone, solvents that produce complexes with titanium such as TBP, DMF, formamide, DMSO and others. Extractants such as the amine extractants that extract both the anion and cation of the titanium salts (thus forming a couple extractant) and acidic extractants such as DEHPA and others.
  • the titanic salt is precipitated from a titanium salt TP1 in solvent solution.
  • the solvent in the titanic salt solution is selected from a group comprising of methanol, ethanol, propanol, butanol or other alkanols, DMSO, N-containing hydrophilic solvents such as DMF, methyl formamide, formamide Pyridine, pyramiding and their derivatives and the combination thereof.
  • the solvent in the titanic salt solution is selected from a group comprising basic extracts and acidic extractants. aln a preferred embodiment the titanic acid is precipitated from aqueous solution. In another preferred embodiment the titanic salt is precipitated from a water poor solution.
  • titanic acid is precipitated from a medium comprising of organic solvent.
  • the titanium salt TP2 is dried after the dissolution of the titanic acid. Any drying method may be used.
  • drying the titanic acid is done using method selected from washing with a solvent, contact with a gas, contact with a hygroscopic solid, contact with a concentrated solution or drying under vacuum or the combination thereof.
  • titanic acid can be dissolved in acidic solution to produce a titanium containing product TP2.
  • the acid is selected from the group selected from acid halides and other acids with a pK value lower than 2.5 which are chemically stable at the conditions in which the reduction to titanium metal takes place.
  • the titanic acid is dissolved in a solution containing a strong acid. In a more preferred embodiment the titanic acid is dissolved in a solution comprising of acid halide and in a more preferred embodiment the titanic acid is dissolved in HCI solution. In a preferred embodiment the titanic acid is dissolved in aqueous solution. In a more preferred embodiment the titanic acid is dissolved in a solvent with low water content.
  • the titanium containing product solution is dried to remove the water present in solution.
  • titanium containing product TP2 is crystallized to give a solid with low water content.
  • titanium containing product TP2 is crystallized to give a solid with low water content
  • titanium containing product TP2 is crystallized to give a solid solvate wherein the solvate is selected from the group comprising of the acid HX or the solvent and the combination thereof.
  • TP2 is not solvated.
  • the product TP2 is selected from a group comprising of titanium salts.
  • the anion of the salt present in the salt TP2 is a mono valent anion. In a more preferred embodiment the anion of the salt TP2 is a halogen. In a more preferred embodiment the anion salt TP2 is Cl.
  • Reduced titanium salts (such as TiCI 3 , TiCI 2 TiBr 3 and TiBr 2 )
  • the product TP is produced by a thermal decomposition of TiOX 2 .
  • TP3 is the titanium salt TP2.
  • the thermal decomposition of TiOX 2 is performed in medium comprising of TiOX 2 , HF, fluoride containing salt and the combination thereof
  • the product TP is produced by a thermal decomposition of TiX 3
  • the thermal conversion temperature is higher than 55O 0 C. In a more preferred embodiment the temperature is higher than 600 0 C In another embodiment the product TP is produced by a thermal.
  • TiCI 3 is reacted with Ti ⁇ 2 at temperature higher than 500 0 C. In amore preferred embodiment the reaction is performed at temperature higher than 65O 0 C
  • TiCI 3 is reacted with O 2 at temperature higher than 500 0 C. In amore preferred embodiment the reaction is performed at temperature higher than 65O 0 C.
  • TiX 3 is reacted with HX at temperature higher than 25O 0 C. In a more preferred embodiment the reaction is performed at temperature higher than 400 0 C.
  • the product TiO 2 is converted to rutile at temperature higher than 600 0 C.
  • the product TiO 2 is converted to TP using a process comprising: i. Leaching with a solution comprising of a strong acid having a pK value higher than 2.5; and ii. Formation of particles comprising of TiOX 2 .
  • the product TiO 2 is reacted with a divalent titanium salt TiX 2 at temperature higher than 500 0 C.
  • a divalent titanium salt TiX 2 at temperature higher than 500 0 C.
  • reaction described in Eq. 8 is higher than 600 0 C.
  • the product TiO 2 is converted to TP using a process comprising of the steps
  • the product TiCI 2 is converted to TP using a process comprising the steps of:
  • TiX 4 can be reduced to Ti(III) using the various reducing agents. There was no indication in the scientific literature that the same can be done using the titanyl (TiOX 2 ) salts as the raw material.
  • titanyl salts can be reduced using hydrogen to give TiOX (tested with Ti 2 OSO 4 or Titanyl halogens such as TiOCI 2 ).
  • the reaction proceeds very well with hydrogenation catalysts even at room temperature in aqueous or in solvent solutions. If the reduction is done in a very acidic solution, TiX 3 is produced instead of TiOX.
  • Ti(IV) salt is reduced to Ti(III) salt.
  • the reduction is done in solution comprising of TiOX 2 , hydrogen and a hydrogenation catalyst and the combination thereof.
  • Ti(IV) salt is reduced to give a Ti(III) salt by adding a reducing agent to a medium comprising of Ti(IV) salt.
  • TP2 is converted to the product TP via the following route:
  • the water is removed during second stage 2 or between the second and the third stages.
  • the anion X in Eq. 1- X is an anion, preferable a mono-valent anion, more preferable an anion selected from the group of halogens and the combination thereof and more preferable selected from the group composed of Cl or Br and the combination thereof.
  • the reductant is H 2 and the reduction is done with a catalyst.
  • the reductant is a metal
  • the reductant is selected from the group comprising of titanium, magnesium, Sodium, iron and the combination thereof.
  • the reductant is selected from a group comprising of an inorganic or organic reducing agent compound or the combination thereof.
  • the reductant in Eq 17 is TiX 2 .
  • TP is produced in a process comprising the steps of:
  • Titanyl salts produced from reacting titanic acid with acids and especially the titanyl halides contain a significant amount of water. Due to its hygroscopic nature it is very difficult to remove the water. The thermal conversion of titanyl salts usually lead to the reaction
  • thermal conversion product is TiO 2 .
  • TiOX 2 produced via the titanic acid route can be dried from water to such a level that it can be used for the thermal conversion reaction to form the TP product - TiX 4 .
  • anion in equations 1-25 is selected from the group comprising of Cl, Br, I and F and the combination thereof.
  • the product TP in equations 1-25 is selected from the group comprising of TiCI 4 , TiBr 4 , TiI 4 and TiF 4 and the combination thereof
  • the temperature in the parr is than increased to 500 0 C.
  • the gas exiting the parr unit is cooled and found to be TiBr 4.
  • After 3 hours the parr unit is cooled and opened. Solid particles are present in the parr. The solid is found to be TiBr 2 .
  • 10gr of TiBr 2 produced in the previous step is introduced into a ceramic tube.
  • the tube is heated to 90O 0 C.
  • the gas exiting the tube is cooled and analyzed and is found to be TiBr 4 .
  • the tube is cooled to RT. Titanium metal is found in the tube.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention porte sur un procédé pour la production industrielle d'un sel de titane TP. Ce procédé comprend les étapes de: i. Précipitation d'acide titanique à partir d'une solution comprenant un sel de titane TP1; ii. Production d'un produit contenant du titane TP2 à partir d'un milieu se composant dudit acide titanique et d'un acide; et iii. Conversion thermique de produit contenant du titane TP3 en un sel de titane TP à une température supérieure à 17Oº C.
PCT/IL2008/000889 2007-06-28 2008-06-29 Procédé de fabrication de sels de titane WO2009001365A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP08763645A EP2173662A1 (fr) 2007-06-28 2008-06-29 Procédé de fabrication de sels de titane
US12/666,947 US8628736B2 (en) 2007-06-28 2008-06-29 Process for the production of titanium salts
CN2008801005503A CN101918318A (zh) 2007-06-28 2008-06-29 生产钛盐的方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IL184311 2007-06-28
IL184311A IL184311A0 (en) 2007-06-28 2007-06-28 A process for the production of titanium salts
IL192452A IL192452A (en) 2007-06-28 2008-06-26 A process for producing titanium salts
IL192452 2008-06-26

Publications (2)

Publication Number Publication Date
WO2009001365A1 true WO2009001365A1 (fr) 2008-12-31
WO2009001365A4 WO2009001365A4 (fr) 2009-03-05

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US (1) US8628736B2 (fr)
EP (1) EP2173662A1 (fr)
CN (1) CN101918318A (fr)
WO (1) WO2009001365A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111545551A (zh) * 2020-05-14 2020-08-18 攀钢集团钛业有限责任公司 氯化收尘渣处理装置及处理方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7272752B2 (ja) * 2018-03-26 2023-05-12 株式会社大阪チタニウムテクノロジーズ 金属チタン製造方法
CN111097915B (zh) * 2020-02-24 2021-05-14 北京科技大学 一种制备低氧高质量氢化脱氢钛粉的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE505183A (fr) *
EP0005018A1 (fr) * 1978-04-21 1979-10-31 Laporte Industries Limited Procédé pour la production de chlorures de titane
US20060062722A1 (en) * 2004-09-20 2006-03-23 Tonyong Applied Materials Technology Corp. Ltd. Method for preparing barium titanate

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2608464A (en) * 1950-08-10 1952-08-26 Nat Lead Co Preparation of titanium and zirconium tetrahalides
US4112045A (en) * 1972-10-05 1978-09-05 Asahi Kasei Kogyo Kabushiki Kaisha Separation of uranium isotopes using anion exchangers
BE1006054A3 (fr) * 1992-07-03 1994-05-03 Solvay Procede de fabrication d'une solution aqueuse d'hydroxyde de sodium.
JP5102770B2 (ja) * 2005-10-11 2012-12-19 ヨマ インターナショナル アーエス チタン製品の製造プロセス
US8133194B2 (en) * 2006-02-22 2012-03-13 Henry Ford Health System System and method for delivery of regional citrate anticoagulation to extracorporeal blood circuits

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE505183A (fr) *
EP0005018A1 (fr) * 1978-04-21 1979-10-31 Laporte Industries Limited Procédé pour la production de chlorures de titane
US20060062722A1 (en) * 2004-09-20 2006-03-23 Tonyong Applied Materials Technology Corp. Ltd. Method for preparing barium titanate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111545551A (zh) * 2020-05-14 2020-08-18 攀钢集团钛业有限责任公司 氯化收尘渣处理装置及处理方法

Also Published As

Publication number Publication date
CN101918318A (zh) 2010-12-15
WO2009001365A4 (fr) 2009-03-05
US20100257977A1 (en) 2010-10-14
EP2173662A1 (fr) 2010-04-14
US8628736B2 (en) 2014-01-14

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